EP0787581A1 - Etiquette pour étiquetage dans le moule et récipient décoré avec cell-ci - Google Patents

Etiquette pour étiquetage dans le moule et récipient décoré avec cell-ci Download PDF

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Publication number
EP0787581A1
EP0787581A1 EP96113070A EP96113070A EP0787581A1 EP 0787581 A1 EP0787581 A1 EP 0787581A1 EP 96113070 A EP96113070 A EP 96113070A EP 96113070 A EP96113070 A EP 96113070A EP 0787581 A1 EP0787581 A1 EP 0787581A1
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EP
European Patent Office
Prior art keywords
label
resin
mold
layer
container
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96113070A
Other languages
German (de)
English (en)
Other versions
EP0787581B1 (fr
Inventor
Akihiko Oji-Yuka Synthetic Paper Co. Ltd. Ohno
Takatoshi Oji-Yuka Synth Paper Co Ltd Nishizawa
Masaki c/o Oji-Yuka Synth. Paper Co. Ltd Shiina
Junichi Oji-Yuka Synthetic Paper Co. Ltd Yasuda
Hajime c/o Mitsubishi Chemical Corporation Ikeno
Keiko Mitsubishi Chemical Corporation Shichijo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yupo Corp
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Yupo Corp
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/24—Lining or labelling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/0864—Applied in mould
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/744—Labels, badges, e.g. marker sleeves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G01N2030/3084—Control of physical parameters of the fluid carrier of temperature ovens
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the present invention relates to a label for use in in-mold molding in which the label is initially set in a mold so that the side of the label which is in contact with the mold wall surface contains printed matter, and a parison of a molten thermoplastic resin is introduced into the mold and molded by blow molding or a molten thermoplastic resin sheet is molded in the mold by vacuum forming or air pressure forming to produce a labeled container.
  • a conventional integral molding process for producing a labeled resin container comprises initially inserting a blank or a label in a mold and then molding a container by injection molding, blow molding, differential pressure forming, foam molding, etc., to decorate the container within the mold [see JP-A-58-69015 (the term "JP-A” as used herein means an "unexamined published Japanese patent application”) JP-A-59-198149 and EP-A-254923].
  • Such known in-mold labels include gravure printed resin films, multicolor offset printed synthetic papers [see, for example, JP-B-2-7814 (the term “JP-B” as used herein means an “examined Japanese patent publication”) and JP-A-2-84319], and gravure printed aluminum labels comprising an aluminum foil laminated on the back side thereof with high pressure low density polyethylene and an ethylene/vinyl acetate copolymer.
  • the label sheet (a sheet of the label material which can be punched or cut to yield a plurality of labels) has poor suitability for feeding and removal in printing (offset, flexographic, UV offset or letterpress printing) in a label production process, and the labels obtained through cutting or punching suffer blocking at their cut edges or are apt to suffer blocking when piled up.
  • An object of the present invention is to provide an in-mold label which shows satisfactory adhesion to a container made of either high density polyethylene or polypropylene, can be easily punched out of a label sheet without forming burrs, and can be easily fed into a mold.
  • the present invention provides an in-mold label comprising a thermoplastic resin film base layer (I) (hereinafter often simply base layer (I)'') carrying printed matter on its front side and, formed on the back side of the base layer (I), a heat sealable resin layer (II) having a lower melting point than the constituent resin of the resin film base layer (I), the constituent resin of the heat sealable resin layer (II) comprising as the main component an ethylene/ ⁇ -olefin copolymer obtained by copolymerizing from 40 to 98 wt% ethylene and from 60 to 2 wt% of an ⁇ -olefin (so as to total 100 wt%) having from 3 to 30 carbon atoms using a metallocene catalyst.
  • a thermoplastic resin film base layer (I) hereinafter often simply base layer (I)'') carrying printed matter on its front side and, formed on the back side of the base layer (I)
  • a heat sealable resin layer (II) having a lower melting point than
  • Another object of the present invention is to provide a container decorated with the label.
  • Fig. 1 is a sectional view of an in-mold label.
  • Fig. 2 is an enlarged plan view of the in-mold label of Fig. 1, viewed from the back side which shows the results of measurement with a surface roughness meter.
  • Fig. 3 is an enlarged sectional view of part of the in-mold label of Fig. 1.
  • Fig. 4 shows a TREF curve
  • Figs. 5, 6, 7 and 8 are differential and integral elution curves.
  • Fig. 9 is a flow sheet illustrating an apparatus for use in the temperature rising elution fractionation (TREF) of resins (i.e., a crystallizability fractionation device).
  • TEZ temperature rising elution fractionation
  • Fig. 1 is a sectional view of an in-mold label for blow molding.
  • numeral 1 denotes the label
  • 2 a thermoplastic resin film base layer (I)
  • 3 printed matter
  • 4 a heat sealable resin layer (II).
  • the heat sealable resin layer (II) may be embossed to avoid label blistering after application to a container (see U.S. Patent 4,986,866 and JP-A-3-260689).
  • Numeral 5 denotes the top of an embossed pattern and 6 denotes a valley thereof.
  • Fig. 2 is a plan view of the label 1, viewed from the side of the heat sealable resin layer 4 (from the back side of the label).
  • Fig. 3 is an enlarged sectional view of part of the label.
  • Figs. 4, 5, 6, 7 and 8 are differential and integral elution curves.
  • Fig. 9 is a crystallizability fractionation device.
  • the label base layer (I) can be a thermoplastic resin layer as is conventionally used as a label base.
  • a resin film having a melting point of from 135 to 264°C e.g., polypropylene, high density polyethylene, poly(vinyl chloride), poly(ethylene terephthalate), or a polyamide
  • Patent 4,318,950 a coated film obtained by coating the above-described resin film or synthetic paper with a latex containing an inorganic filler (coating material); a base comprising a vapor deposited aluminum layer formed on any of the above described films; and a laminate of any of the above described films with an aluminum foil.
  • a microporous laminate resin film comprising a biaxially stretched film base layer (A) comprising from 5 to 30 wt% fine inorganic particles, from 3 to 20 wt% high density polyethylene, and from 92 to 50 wt% polypropylene resin, a paper-like layer (B) made of a uniaxially stretched film of a resin composition comprising from 35 to 65 wt% fine inorganic particles, from 0 to 10 wt% high density polyethylene, and from 55 to 35 wt% polypropylene resin, and a paper-like layer (C) made of a uniaxially stretched film of a resin composition comprising from 35 to 65 wt% fine inorganic particles, from 0 to 10 wt% high density polyethylene, and from 55 to 35 wt% polypropylene resin.
  • A biaxially stretched film base layer
  • A biaxially stretched film base layer
  • B made of a uniaxially stretched film of a resin composition comprising from 35 to 65 wt
  • the paper-like (B) is laminated to one side of the base layer (A) and the paper-like layer (C) is laminated to the base layer (A) on the side opposite to the paper-like layer (B).
  • the thickness of the base layer (A) is preferably from 30 to 150 ⁇ m, and the thickness of the paper layer (B) and (C) is each from 0.5 to 40 ⁇ m.
  • the base layer (I) further include a base layer film having a layer for density regulation formed between the above-described base layer (A) and paper-like layer (B).
  • this type of base layer is, for example, a microporous laminate resin film comprising a biaxially stretched film base layer (A) comprising from 5 to 30 wt% fine inorganic particles, from 3 to 20 wt% high density polyethylene, and from 92 to 50 wt% polypropylene resin, a paper-like layer (C) made of a uniaxially stretched film of a resin composition comprising from 35 to 65 wt% fine inorganic particles, from 0 to 10 wt% high density polyethylene, and from 55 to 35 wt% polypropylene resin, an interlayer (D) laminated to the base layer (A) on the side opposite to the paper-like layer (C) made of a uniaxially stretched film of a resin composition comprising from 35 to 65 wt% fine inorganic particles, from
  • the paper like layer (B) contains from 3 to 35 wt% more fine inorganic particles than those in the interlayer (D).
  • Either of these types of microporous stretched laminate resin films i.e., with or without interlayer (D) have a density of from 0.65 to 1.02 g/cm 3 and a porosity of 5 to 55%, preferably 15 to 45%.
  • printed material is formed on the paper-like layer (B) side and a heat sealable resin layer (II) is formed on the paper-like layer (C) side.
  • the thickness of the base layer (I) is from 20 to 200 ⁇ m, preferably from 40 to 150 ⁇ m.
  • the heat sealable resin layer (II) comprises as the main component an ethylene/ ⁇ -olefin copolymer obtained by copolymerizing from 40 to 98 wt% ethylene and from 60 to 2 wt% of an ⁇ -olefin (total: 100 wt%) having from 3 to 30 carbon atoms using a metallocene catalyst.
  • This ethylene/ ⁇ -olefin copolymer preferably satisfies the following property requirements (1), (2) and (3):
  • An especially preferred material of the heat sealable resin layer (II) is a resin composition comprising:
  • the ethylene/ ⁇ -olefin copolymer of ingredient (a), which is a type of a linear low density polyethylene, is obtained by copolymerizing a major proportion of ethylene and a minor proportion of an ⁇ -olefin using a metallocene catalyst.
  • the catalyst include metallocene/aluminoxane catalysts and catalysts comprising a combination of a metallocene compound (such as that disclosed in, e.g., International Publication WO 92/01723) and a compound of the formula ML x (hereinafter described) which reacts with the metallocene compound to change such compound into a stable anion.
  • Ethylene is used in a proportion of from 40 to 98 wt%, preferably from 50 to 95 wt%, and most preferably from 70 to 93 wt%, balance ⁇ -olefin so as to total 100 wt%.
  • Examples of the ⁇ -olefin having from 3 to 30 carbon atoms which is copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methylpentene-1, 4-methylhexene-1, 4,4-dimethylpentene-1, and octadecene. Preferred of these are 1-hexene, 1-octene, 1-heptene, and 4-methylpentene-1.
  • the ⁇ -olefin is used in a proportion of from 2 to 60 wt%, preferably from 5 to 50 wt%, and most preferably from 7 to 30 wt%.
  • metallocene catalyst examples include metallocene compounds represented by the following formula. ML x
  • M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta, and Cr; each L is a ligand coordinated to the transition metal, at least one of which is a ligand having a cyclopentadienyl skeleton, with the balance (if any) being a hydrocarbon group having from 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO 3 R group (where R is a hydrocarbon group having from 1 to 8 carbon atoms and optionally substituted with, e.g., a halogen), a halogen atom, or a hydrogen atom; and x is the valence of the transition metal.
  • Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, alkyl-substituted cyclopentadienyl groups such as methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, methylethylcyclopentadienyl, propylcyclopentadienyl, methylpropylcyclopentadienyl, butylcyclopentadienyl, methylbutylcyclopentadienyl, and hexylcyclopentadienyl; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; and a fluorenyl group. These groups may be substituted
  • alkyl-substituted cyclopentadienyl groups are alkyl-substituted cyclopentadienyl groups.
  • two of these groups may be bonded to each other through an alkylene group, e.g., ethylene or propylene, a substituted alkylene group, e.g., isopropylidene or diphenylmethylene, a silylene group, a substituted silylene group, e.g., dimethylsilylene, diphenylsilylene or methylphenylsilylene.
  • Examples of the ligands other than the ligands having a cyclopentadienyl skeleton include the following.
  • Examples of the hydrocarbon group having from 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups.
  • Examples of the alkyl groups include methyl, ethyl, propyl, isopropyl and butyl.
  • Examples of the cycloalkyl groups include cyclopentyl and cyclohexyl.
  • Examples of the aryl groups include phenyl and tolyl.
  • Examples of the aralkyl groups include benzyl and neophyl.
  • Examples of the alkoxy groups include methoxy, ethoxy and butoxy.
  • Examples of the aryloxy groups include phenoxy.
  • Examples of the halogen include fluorine, chlorine, bromine and iodine.
  • Examples of the ligand represented by SO 3 R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.
  • metallocene compounds containing at least one ligand having a cyclopentadienyl skeleton can be more specifically represented by the following formula, in the case where the transition metal has a valence of, for example, 4.
  • M is the transition metal as earlier described;
  • R 2 is a group (ligand) having a cyclopentadienyl skeleton as earlier described;
  • R 3 , R 4 , and R 5 each is a group having a cyclopentadienyl skeleton as earlier described, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO 3 R group, a halogen atom or a hydrogen atom as earlier described;
  • Preferred metallocene compounds for use in the present invention are represented by the above formula R 2 k R 3 l R 4 m R 5 n M where at least two of R 2 , R 3 , R 4 , and R 5 , i.e., R 2 and R 3 , each is a group (ligand) having a cyclopentadienyl skeleton.
  • These groups having a cyclopentadienyl skeleton may be bonded to each other through an alkylene group, e.g., ethylene or propylene, a substituted alkylene group, e.g., isopropylidene or diphenylmethylene, a silylene group, a substituted silylene group, e.g., dimethylsilylene, diphenylsilylene or methylphenylsilylene, or another group.
  • alkylene group e.g., ethylene or propylene
  • a substituted alkylene group e.g., isopropylidene or diphenylmethylene
  • silylene group e.g., a substituted silylene group, e.g., dimethylsilylene, diphenylsilylene or methylphenylsilylene, or another group.
  • R 4 and R 5 each is a group having a cyclopentadienyl skeleton, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO 3 R, a halogen atom or a hydrogen atom.
  • transition metal compounds wherein M is zirconium include bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconium bis(p-toluenesulfonate), bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium bis(methanesulfonate), ethylenebis(indenyl)zirconium bis(p-toluenesulfonate),
  • the disubstituted cyclopentadienyl rings include 1,2-substituted and 1,3-substituted rings, while the trisubstituted cyclopentadienyl rings include 1,2,3-substituted and 1,2,4-substituted rings.
  • the alkyl groups such as propyl and butyl include n-, i-, sec-, tert-, and other isomers.
  • the zirconium atom has been replaced with a titanium, hafnium, vanadium, niobium, tantalum or chromium atom. All of these compounds may be used alone or as a combination of two or more thereof. They may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
  • the metallocene compound is preferably a zirconocene compound in which the central metal atom is zirconium and which has at least two ligands each having a cyclopentadienyl skeleton.
  • Examples of the aluminoxane used in combination with the metallocene compound include aluminoxanes represented by general formulae (1) and (2).
  • R is a hydrocarbon group, e.g., methyl, ethyl, propyl, or butyl, preferably methyl or ethyl, and more preferably methyl, and m is an integer of 2 or larger, preferably from 5 to 40.
  • the aluminoxane may comprise mixed alkyloxyaluminum units consisting of one or more alkyloxyaluminum units represented by the formula (OAl(R 1 )) and one or more alkyloxyaluminum units represented by the formula (OAl(R 2 )), where R 1 and R 2 each is a hydrocarbon group, examples of which are the same as those given with regard to R, provided that R 1 and R 2 represent different groups.
  • the aluminoxane desirably comprises mixed alkyloxyaluminum units containing one or more methyloxyaluminum units (OAl(CH 3 )) in an amount of 30 mol% or larger, preferably 50 mol% or larger, especially preferably 70 mol% or larger.
  • aluminoxane For producing such an aluminoxane, the following methods can, for example, be used.
  • the aluminoxane may contain a small amount of organometallic ingredients other than aluminum compounds. After the solvent or the unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent such as a hydrocarbon or halogenated hydrocarbon.
  • organoaluminum compound used for producing an aluminoxane examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and di
  • organoaluminum compound isoprenylaluminums represented by the following formula. (i-C 4 H 9 ) x Al y (C 5 H 10 ) z
  • x, y, and z each is a positive number, and z ⁇ 2x.
  • organoaluminum compounds are trialkylaluminums.
  • organoaluminum compounds enumerated above may be used alone or in combination.
  • Examples of the solvent or media used for producing an aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and gas oil; halides, in particular chlorides and bromides, of the above enumerated aromatic, aliphatic, and alicyclic hydrocarbons; and ethers such as ethyl ether and tetrahydrofuran. Especially preferred of these are aromatic hydrocarbons.
  • the proportion of the aluminum contained in the aluminoxane to all of the metal contained in the metallocene is about from 0.5:1 to 10,000:1, preferably about from 5:1 to 1,000:1.
  • the compound which reacts with a metallocene compound to change the compound into a stable anion is either an ionic compound made up of a cation and an anion or an electrophilic compound.
  • the ionic or electrophilic compound changes into a stable ion to form an active species which catalyzes polymerization.
  • the ionic compound is represented by the following formula. [Q] m+ [Y] m-
  • Q is the cation component of the ionic compound, examples of which include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation and a phosphonium cation.
  • examples of the cation component further include metallic and organometallic cations which themselves are susceptible to reduction.
  • JP-W cations capable of yielding protons
  • JP-W-1-501950 the term “JP-W” as used herein means an "unexamined published Japanese patent application based on an international patent application
  • JP-W may be cations which do not yield protons.
  • Such cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N,N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri(dimethylphenyl)phosphonium, tri(methylphenyl)phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, mercury ion and ferrocenium ion.
  • Y is the anion component of the ionic compound. It changes into a stable anion upon reaction with a metallocene compound.
  • the anion include organoboron compound anions, organoaluminum compound anions, organogallium compound anions, organphosphorus compound anions, organoarsenic compound anions, and organoantimony compound anions.
  • tetraphenylboron tetrakis(3,4,5-trifluorophenyl)boron, tetrakis(3,5-di(trifluoromethyl)phenyl)boron, tetrakis(pentafluorophenyl)boron, tetraphenylaluminum, tetrakis(3,4,5-trifluorophenyl)aluminum, tetrakis(3,5-di(trifluoromethyl)phenyl)aluminum, tetrakis(pentafluorophenyl)aluminum, tetraphenylgallium, tetrakis(3,4,5-trifluorophenyl)gallium, tetrakis(3,5-di(trifluoromethyl)phenyl)gallium, tetrakis(3,5-di(t-butyl)phenyl)gallium, tetrakis(
  • m is a cardinal number such as 1, 2, 3, 4, etc., of the ion value of Q and Y.
  • the electrophilic compound is a compound which is known as a Lewis acid and it reacts with a metallocene compound to change the electrophilic compound into a stable anion and form an active species which catalyzes polymerization.
  • the electrophilic compound include various metal halide compounds and metal oxides known as solid acids. Specific examples thereof include magnesium halides such as MgCl 2 and inorganic compounds known as Lewis acids.
  • polymerization methods useful herein include vapor phase polymerization, slurry polymerization, solution polymerization and high pressure ionic polymerization. Preferred of these are solution polymerization and high pressure ionic polymerization. In particular, the high pressure ionic polymerization process is preferably used for polymer production.
  • Examples of this high pressure ionic polymerization process include the continuous process for ethylene polymer production described in JP-A-56-18607 and JP-A-58-225106, in which polymerization is conducted under the reaction conditions of a pressure of 100 kg/cm 2 or higher, preferably from 200 to 2,000 kg/cm 2 , and a temperature of 125°C or higher, preferably from 130 to 250°C, and more preferably from 150 to 200°C.
  • ethylene/ ⁇ -olefin copolymers obtained with such metallocene catalysts is an ethylene/ ⁇ -olefin copolymer which is obtained with a catalyst comprising a combination of a metallocene compound and an ionic compound represented by the earlier described formula [Q] m+ [Y] m- and which satisfies the following property requirements (1) to (3) and preferably further satisfies the property requirements (4) and (5).
  • MFR melt flow rate
  • Copolymers having an MFR higher than the upper limit show unstable film formation, while copolymers having an MFR lower than the lower limit suffer film breakage during molding.
  • Copolymers having a density higher than the upper limit have poor low temperature heat sealability, while copolymers having too low a density give films which have surface tackiness and are unable to be put to practical use.
  • the lower limit of the density is usually about 0.86 g/cm 3 .
  • the ethylene/ ⁇ -olefin copolymer gives an elution curve which has one peak, where the peak temperature is from 20 to 85°C, preferably from 30 to 75°C, most preferably from 40 to 70°C, and the value of [the peak height]/[the peak width at half height] (H/W) is 1 or more, preferably from 1 to 20, more preferably from 1 to 15, and most preferably from 1 to 10.
  • the peak temperature is from 20 to 85°C, preferably from 30 to 75°C, most preferably from 40 to 70°C
  • the value of [the peak height]/[the peak width at half height] (H/W) is 1 or more, preferably from 1 to 20, more preferably from 1 to 15, and most preferably from 1 to 10.
  • one peak means one projecting portion in the figure drawn as a bird's-eye view as shown in Fig. 5 or 6. Such a projecting portion may have small projecting portions b, c with easy or gradual undulations as shown in Fig. 5.
  • the elution curve may show that the copolymer contains one or more components which are eluted at a temperature other than the peak elution temperature (see Fig. 4, (b) and (c), and Fig. 5).
  • a projecting portion comprising two peaks and a valley therebetween as shown in Fig. 7, and a pair of projecting portions, completely separated from each other, however, fall outside the scope of the definition of the word "one peak”.
  • the copolymer If the peak temperature of the elution curve exceeds the upper limit, the copolymer has poor low temperature heat sealability and is hence unsuitable for practical use.
  • the copolymer comes to have poor heat sealability with the passage of time due to a large proportion of tacky components contained therein and is hence unsuitable for practical use.
  • the temperature rising elution fractionation for determining an elution curve is carried out according to Journal of Applied Polymer Science , Vol. 26, pp. 4217-4231 (1981), hereby incorporated by reference.
  • a cross fractionator is used which has three independent ovens [a column oven for TREF (packed with glass beads heated to 140°C), a valve oven, and an SEC column oven] as shown in Fig. 9.
  • the ethylene resin to be analyzed is dissolved in a solvent, e.g., o-dichlorobenzene, with heating (140°C), and this resin solution is injected into a sample loop (f) through a sample valve (e) with a syringe (d).
  • a solvent e.g., o-dichlorobenzene
  • An injection valve (g) is operated first, followed by operation of a sample valve (e). After a given volume (0.5 ml) of the solution has been injected into the sample loop (f), the sample valve (e) recovers its original position, and the solution in the sample loop is introduced into the center of a TREF column (h), whereupon the injection valve (g) returns to its original position.
  • the TREF column is cooled from 140°C to 0°C at a rate of 1°C/min, and the resin deposits on the surface of the carrier (glass beads) packed in the column (this polymer layer deposition on the glass bead surface occurs in the range from highly crystalline (high elution temperature) components to slightly crystalline (low elution temperature) components).
  • the TREF column After the TREF column is cooled to 0°C, it is maintained at this temperature for a given period (30 minutes). Any resin component which is in a dissolved state at that temperature is sent from the TREF column to an SEC column at a flow rate of 1 ml/min by operating the injection valve (g). Thereafter, molecular sieve fractionation is conducted in the SEC column, during which the TREF column is gradually heated from 0°C to 140°C, while being maintained at each of the following temperatures for 30 minutes.
  • the TREF column is heated to the next predetermined temperature and maintained at this temperature, during which time the molecular sieve fractionation of the resin solution which has been injected into the SEC column is conducted in the column (the analysis of each elution fraction in the SEC column is performed at an interval of 39 minutes). Data regarding a chromatogram are stored in a computer.
  • the solution separated is analyzed with an infrared detector (p) to determine the resin concentration. Thereafter, the injection, heating, and molecular sieve fractionation are repeated.
  • Fig. 9 denotes a solvent tank, (b) an auxiliary pump, (c) a pump, (d) a syringe, (e) a six-way sample valve, (f) a sample loop, (g) an injection valve, (h) a TREF column, (i) a six-way valve, (j) an initial standard solution loop, (k) a tank, (l) a stop valve, (m) a three-way valve, (n) an internal filter, (o) an SEC column, (p) an infrared detector, (q) a stop valve, and (r) a waste liquid tank.
  • the data stored in the computer are processed and outputted as differential and integral elution curve (see Fig. 4).
  • a base line of the chromatogram for each elution temperature obtained in the above analysis is drawn, and arithmetic processing is conducted.
  • the area of each chromatogram is integrated to calculate an integral elution curve.
  • This integral elution curve is differentiated with temperature to calculate a differential elution curve.
  • non-crystalline components of the ethylene resin i.e., ethylene resin components having a high degree of branching of short branch chains, dissolve first in a low temperature range. As the elution temperature rises, components having a lower degree of branching gradually dissolve. Finally, linear ethylene resin components having no branches dissolve, whereupon the analysis is terminated.
  • a cross fractionator CFCT150A (trade name), manufactured by the Mitsubishi Chemical Corporation, was used, in which the TREF column was packed with glass beads as an inactive carrier.
  • the SEC column used was composed of three AD80M/S (trade name) columns, manufactured by Showa Denko K.K., arranged in series and packed with a polystyrene gel.
  • the resin solution to be injected into the sample loop (f) of the cross fractionator was prepared by dissolving the ethylene resin in o-dichlorobenzene in such an amount as to result in a resin concentration of 4 mg/ml, and was injected in an amount of 0.4 ml.
  • the integral elution amount determined by integrating the weight proportion of eluted components up to an elution temperature of 10°C is 10% or less, and that amount determined to an elution temperature of 90°C is 90% or more, preferably the integral elution amount to an elution temperature of 20°C is 10% or less and that to an elution temperature of 90°C is 95% or more, and most preferably the integral elution amount to an elution temperature of 20°C is 5% or less and that to an elution temperature of 90°C is 97% or more.
  • the ethylene/ ⁇ -olefin copolymer of the present invention gives a Q value (weight average molecular weight/number average molecular weight) as determined by size exclusion chromatography (SEC) of 4 or less, preferably 3 or less, more preferably 2.5 or less.
  • Q value weight average molecular weight/number average molecular weight
  • MFR 190°C, 2.16 kg load
  • ASTM D-569 an MFR (190°C, 2.16 kg load) as measured in accordance with ASTM D-569 of from 0.1 to 20 g/10 min, preferably from 1 to 13 g/10 min, and more preferably from 2 to 13 g/10 min.
  • Polyethylenes having an MFR higher than the upper limit result in unstable film formation, while polyethylenes having an MFR lower than the lower limit have poor extrudability and yield a film of poor appearance.
  • Polyethylenes having a density higher than the upper limit have poor low temperature heat sealability, while polyethylenes having a density lower than the lower limit yield films whose surface is too tacky.
  • ME (3 g) 1.6 or higher, preferably 1.8 or higher, more preferably 2.0 or higher, and most preferably from 2.3 to 5.
  • Polyethylenes having an ME lower than the lower limit are undesirable in that they provide unstable film formation.
  • ME 3 g
  • JIS K7210 melt indexer according to JIS K7210 under the conditions of a cylinder temperature of 240°C and a constant extrusion rate of 3 g/min as follows.
  • a sample is packed into the apparatus, and only the piston is placed thereon. Six minutes thereafter, the sample begins to be extruded at a predetermined rate. Subsequently, a measuring flask filled with ethyl alcohol is placed directly under the orifice to obtain a straight extrudate.
  • the diameter (D) of the extrudate is measured with a micrometer.
  • an MT of 1.5 g or higher preferably 2.5 g or higher, more preferably from 5 g to 15 g.
  • Polyethylenes having too low an MT are undesirable in that the effect of improving processability is reduced.
  • the high pressure low density polyethylene for use in the present invention has an ME (3 g) and an MT which both satisfy the following relationship.
  • This high pressure low density polyethylene has a Q value (weight average molecular weight/number average molecular weight) as determined by size exclusion chromatography (SEC) of from 5 to 30, preferably from 7 to 25, most preferably from 10 to 20.
  • Q value weight average molecular weight/number average molecular weight
  • an especially preferred high pressure low density polyethylene is one produced in an autoclave at a reaction temperature of 220°C or higher and a reaction pressure of 1,700 kg/cm 2 or lower.
  • the ethylene/ ⁇ -olefin copolymer (a) is blended with the high pressure low density polyethylene (b) in such a ratio that the proportions of ingredient (a) and ingredient (b) are from 50 to 90 wt% and from 10 to 50 wt%, respectively, preferably from 55 to 90 wt% and from 10 to 45 wt%, respectively, and more preferably from 60 to 85 wt% and from 15 to 40 wt%, respectively, an totally 100 wt%.
  • This heat sealable resin composition comprising ingredients (a) and (b) preferably has an MFR of from 5 to 25 g/10 min, more preferably from 8 to 20 g/10 min, a density of from 0.87 to 0.932 g/cm 3 , preferably from 0.89 to 0.912 g/cm 3 , a Q value of from 2 to 10, preferably from 3 to 6, an ME (3 g) of from 1.2 to 2.3, preferably from 1.5 to 2.0, and an MT of 1.0 g to 6 g, preferably 1.5 g or higher, where all test procedures to determine these parameters have been earlier given, with ME and MT satisfying the following relationship.
  • the heat-sealable layer (II) has a lower melting point than the base layer (I).
  • the melting point of the heat-sealable layer (II) is lower by about 8°C to about 150°C than that of the base layer (I).
  • the heat-sealable resin layer (II) in accordance with the present invention has a thickness of from 1 to 10 ⁇ m, preferably from 2 to 8 ⁇ m.
  • the thickness thereof should be at least 1 ⁇ m in order for the adhesive layer film to melt during blow molding by the thermal action of the parison of molten polyethylene or polypropylene to provide tenacious adhesion between the label and the molding. Thicknesses thereof exceeding 10 ⁇ m are undesirable in that label curling occurs to cause difficulties in offset printing and in label fixing to a mold.
  • the heat-sealable resin layer of the label is preferably embossed in order to avoid blistering during blow molding, as described in JP-A-2-84319 and JP-A-3-260689.
  • an embossed pattern having from 5 to 25 lines per 2.54 cm is formed, with the depth of the valleys thereof being from 1 to 8 ⁇ m and being at least 1/3 of the thickness of the heat-sealable resin layer. Embossing is unnecessary for labels for injection molding.
  • Corona discharge treatment or the like may be conducted, if desired and necessary, to improve the surface printability and adhesion of these in-mold labels.
  • Printed matter can be formed by gravure printing, offset printing, flexographic printing, screen printing, etc. All such procedures are conventional.
  • the print may contain a bar code, a maker's name, a seller's name, be a character, a trademark, usage, and the like.
  • a printed and embossed label (1) is cut into a desired shape and size by punching or any other desired procedure.
  • This in-mold label may have such a size as to cover a part of the surface of a container.
  • the label is produced as a blank for surrounding the side wall of a container cup, or as a label to be applied to the front and back sides of container bottle produced by blow molding.
  • the in-mold label is set in the cavity of the female mold, i.e., the lower mold half, of a differential pressure forming mold in such a manner that the print side of the label is in contact with the cavity wall.
  • the label is then fixed to the inner surface of the mold wall by suction.
  • a sheet or layer of a molten resin which is to form the container is placed over the female mold to conduct differential pressure forming in a conventional way.
  • a labeled container is molded in which the label has been fused to and united with the external surface of the container wall.
  • differential pressure forming may be either vacuum forming or air pressure forming, a combination of both is generally preferably carried out with a plug assist.
  • the labels per the present invention are also applicable to blow molding in which a parison of a molten resin is pressed with air pressure against the inner surface of the mold wall.
  • the labeled container thus produced is free from deformation of the label (1), has excellent adhesion between the container body and the label (1), and has a satisfactory decorative appearance with no blistering, because the label (1) was fixed to the inner surface of the mold before being united with the resin container by integral molding.
  • a catalyst was prepared by the method disclosed in JP-A-61-130314 as follows. To 2.0 mmol of ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride complex was added the methylaluminoxane manufactured by Toyo Stauffer Chemical Co., Ltd., in an amount of 1,000 times by mole the amount of the complex. This mixture was diluted with toluene to a total volume of 10 liters to prepare a catalyst solution. Using this catalyst, polymerization was conducted by the following method.
  • an ethylene/ ⁇ -olefin copolymer (1-hexene content, 22 wt%) was obtained which had an MFR of 18 g/10 min, a density of 0.898 g/cm 3 , a Q value of 1.9 and which gave a TREF elution curve having one peak, with the peak temperature being 50°C and the value of H/W for that peak temperature being 1.5.
  • the integral elution amount to 10°C was 2.1%, that to 20°C was 3.0%, and that to 80°C was 100%.
  • a high pressure low density polyethylene was produced with an autoclave at a polymerization temperature of 260°C and a polymerization pressure of 1,500 kg/cm 2 .
  • the high pressure low density polyethylene thus obtained had an MFR of 4 g/10 min, a density of 0.92 g/cm 3 , an ME of 2.4, an MT of 10.2 g and a Q value of 10.
  • a resin composition (C) consisting of 51.5 parts by weight of polypropylene "MA-3", 3.5 parts by weight of high density polyethylene “EY-40", 42 parts by weight of calcium carbonate particles having a particle diameter of 1.5 ⁇ m, and 3 parts by weight of titanium oxide particles having a particle diameter of 0.8 ⁇ m
  • a resin composition (II) for heat sealable resin layer formation consisting of 75 wt% of the ethylene/ ⁇ -olefin (1-hexene) copolymer obtained in the Production Example 1 given above and 25 wt% of the high pressure low density polyethylene obtained in the Production Example 2 given above were melt kneaded at 200°C using separate extruders.
  • melts were fed to a co-extrusion die and laminated to each other within the die, and the resulting laminate film extruded through the die was extrusion-laminated to the back side of the machine-directionally 5-fold stretched sheet of composition (A).
  • Layer II had an MFR of 13 g/10 min, a density of 0.904 g/cm 3 , an ME of 1.7 and an MT of 1.6 g.
  • Offset printing was conducted on the paper-like layer (B) side of this stretched resin film having the recited laminated four-layer structure.
  • the printed film was passed through embossing rolls to form on the heat-sealable resin layer (II) side an embossed pattern comprising dotted lines at an interval of 1.27 mm (20 lines) and having a valley depth of 8 ⁇ m.
  • An enlarged view of this embossed pattern is shown in Fig. 2.
  • the layer (II) had a Bekk's surface smoothness of 480 seconds.
  • the embossed film was punched to obtain a label (width, 60 mm; length, 110 mm) for blow molding.
  • This label was fixed by suction to one half of a split-cavity mold for blow molding so that the printed side of the label was in contact with the mold.
  • High density polyethylene "Mitsubishi Polyethy HD BZ-53A" (trade name) having a density of 0.960 g/cm 3 , a melt index of 0.8 g/10 min, and a melting point of 134°C was melt-extruded at 230°C to form a parison, and the mold was then closed. Subsequently, air compressed to 4.2 kg/cm 2 was fed into the parison to expand the parison and closely contact the same with the mold. Thus, the parison was formed into a container shape and the label was fused thereto. After cooling, the mold was opened to obtain a labeled hollow container.
  • This labeled hollow container was free from print fading, and underwent neither label shrinkage nor blistering.
  • the adhesion strength between the container and the label was 750 g/15-mm width.
  • the embossed film was then trimmed to obtain an in-mold label sheet having a density of 0.91 g/cm 3 .
  • the heat sealable resin (II) layer of this label sheet had a Bekk's surface smoothness of 750 seconds.
  • In-mold label sheets were obtained in the same manner as in Example 2, except that each of the resin compositions shown in Table 1 was used as the heat-sealable resin composition (II).
  • the label sheets obtained in Examples 3 to 5 and Comparative Examples 1 to 3 were subjected to offset printing, cutting and punching to obtain in-mold labels (1) (width, 60 mm; length, 110 mm). These labels were evaluated for coefficient of friction, suitability for continuous offset printing, and label punchability.
  • each of these in-mold labels (1) was fixed by suction to one half of a split cavity mold for blow molding so that the printed side of the label was in contact with the mold.
  • High density polyethylene (melting point, 134°C) was melt-extruded at 200°C to form a parison, and the mold was then closed. Subsequently, air compressed to 4.2 kg/cm 2 was fed into the parison to expand the parison and closely contact the same with the mold. Thus, the parison was formed into a container shape and the in-mold label was fused thereto. After cooling, the mold was opened to obtain a labeled hollow container.
  • labeled hollow containers were obtained in the same manner as above, except that a propylene homopolymer (melting point, 165°C; MFR, 1.0 g/10 min) was used as a parison material in place of the high-density polyethylene, and melt-extruded at 230°C.
  • a propylene homopolymer melting point, 165°C; MFR, 1.0 g/10 min
  • In-mold labels were obtained which were free from burr generation in punching and showed satisfactory adhesion to polypropylene containers and to high density polyethylene hollow containers.

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WO1998037142A1 (fr) * 1997-02-25 1998-08-27 Exxon Chemical Patents Inc. Scellement de polyethylene a un substrat
EP0949599A2 (fr) * 1998-04-06 1999-10-13 Oji-Yuka Synthetic Paper Co., Ltd. Etiquette pour étiquetage dans le moule
EP0960020A1 (fr) * 1997-01-28 1999-12-01 Avery Dennison Corporation Etiquettes dans le moule et leurs utilisations
EP1013415A2 (fr) * 1998-12-23 2000-06-28 M & W Verpackungen GmbH Etiquette stratifiée pour l'étiquetage dans le moule
WO2001028755A1 (fr) * 1999-10-15 2001-04-26 Trespaphan Gmbh Etiquette a base de film en polyolefine
WO2006053267A1 (fr) * 2004-11-10 2006-05-18 Avery Dennison Corporation Etiquettes surmoulees et leurs utilisations
EP1820822A2 (fr) * 2003-05-08 2007-08-22 Novolen Technology Holdings, C.V. Composition de résine de polypropylène
CH699237A1 (de) * 2008-07-24 2010-01-29 Alpla Werke Kunststoffformulierung und Verfahren zur Herstellung von Kunststoffflaschen in einem Zweistufen-Streckblasprozess.
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US6150013A (en) * 1996-02-23 2000-11-21 Avery Dennison Corporation Low thermal conductivity in-mold label films
US6866938B2 (en) 1997-07-22 2005-03-15 Nissha Printing Co., Ltd. Foil-detecting sheet and method of producing a foil-decorated resin article using the same
WO1999043485A1 (fr) 1998-02-27 1999-09-02 Nissha Printing Co., Ltd. Feuille pour decoration dans le moule et article decore dans le moule
JP2000047588A (ja) * 1998-07-29 2000-02-18 Oji Yuka Synthetic Paper Co Ltd インモールド成形用ラベル
EP1122704A4 (fr) * 1998-10-15 2009-01-28 Yupo Corp Etiquette pour moulage en moule
JP2001030342A (ja) * 1999-07-23 2001-02-06 Japan Polychem Corp ポリオレフィン製延伸ブロー成形用インモールドラベル及びそのラベルを熱融着させた成形体
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JP4803848B2 (ja) * 2009-09-11 2011-10-26 株式会社積水技研 樹脂シートおよび樹脂製容器
JP6103343B2 (ja) * 2012-04-27 2017-03-29 株式会社吉野工業所 インモールド成形用ラベル及びラベル付き容器
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EP0960020A4 (fr) * 1997-01-28 2002-11-20 Avery Dennison Corp Etiquettes dans le moule et leurs utilisations
US7700188B2 (en) 1997-01-28 2010-04-20 Avery Dennison Corporation In-mold labels and users thereof
EP0960020A1 (fr) * 1997-01-28 1999-12-01 Avery Dennison Corporation Etiquettes dans le moule et leurs utilisations
US6726969B1 (en) 1997-01-28 2004-04-27 Avery Dennison Corporation In-mold labels and uses thereof
WO1998037142A1 (fr) * 1997-02-25 1998-08-27 Exxon Chemical Patents Inc. Scellement de polyethylene a un substrat
EP0949599A3 (fr) * 1998-04-06 2000-10-11 Oji-Yuka Synthetic Paper Co., Ltd. Etiquette pour étiquetage dans le moule
EP0949599A2 (fr) * 1998-04-06 1999-10-13 Oji-Yuka Synthetic Paper Co., Ltd. Etiquette pour étiquetage dans le moule
EP1013415A3 (fr) * 1998-12-23 2002-01-30 M & W Verpackungen GmbH Etiquette stratifiée pour l'étiquetage dans le moule
EP1013415A2 (fr) * 1998-12-23 2000-06-28 M & W Verpackungen GmbH Etiquette stratifiée pour l'étiquetage dans le moule
WO2001028755A1 (fr) * 1999-10-15 2001-04-26 Trespaphan Gmbh Etiquette a base de film en polyolefine
US6838042B1 (en) 1999-10-15 2005-01-04 Trespaphan Gmbh Label made of polyolefin film
EP1820822A3 (fr) * 2003-05-08 2008-11-12 Novolen Technology Holdings, C.V. Composition de résine de polypropylène
EP1820822A2 (fr) * 2003-05-08 2007-08-22 Novolen Technology Holdings, C.V. Composition de résine de polypropylène
WO2006053267A1 (fr) * 2004-11-10 2006-05-18 Avery Dennison Corporation Etiquettes surmoulees et leurs utilisations
CN101053004B (zh) * 2004-11-10 2012-01-11 艾利丹尼森公司 模内标签及其用途
CH699237A1 (de) * 2008-07-24 2010-01-29 Alpla Werke Kunststoffformulierung und Verfahren zur Herstellung von Kunststoffflaschen in einem Zweistufen-Streckblasprozess.
GB2592616A (en) * 2020-03-03 2021-09-08 Bockatech Ltd Method of forming an article
WO2021175808A1 (fr) * 2020-03-03 2021-09-10 Bockatech Ltd Procédé de formation d'un article
GB2592616B (en) * 2020-03-03 2023-07-19 Bockatech Ltd Method of forming an article

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AU717211B2 (en) 2000-03-23
US5811163A (en) 1998-09-22
KR970063009A (ko) 1997-09-12
JP3920373B2 (ja) 2007-05-30
JPH09207166A (ja) 1997-08-12
AU6442996A (en) 1997-08-07
ATE254033T1 (de) 2003-11-15
DE69630664T2 (de) 2004-10-07
DE69630664D1 (de) 2003-12-18
KR100443434B1 (ko) 2004-10-22
EP0787581B1 (fr) 2003-11-12

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